CN1207315C - Catalyst for preparing syndiotacti polystyrene - Google Patents

Catalyst for preparing syndiotacti polystyrene Download PDF

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CN1207315C
CN1207315C CN 02111301 CN02111301A CN1207315C CN 1207315 C CN1207315 C CN 1207315C CN 02111301 CN02111301 CN 02111301 CN 02111301 A CN02111301 A CN 02111301A CN 1207315 C CN1207315 C CN 1207315C
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Prior art keywords
catalyzer
syndiotactic polystyrene
cyclopentadienyl
catalyst
alkylaluminoxane
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CN1450093A (en
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沈志刚
林尚安
周文乐
祝方明
赵薇薇
卢文奎
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Priority to US10/410,036 priority patent/US6921734B2/en
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Abstract

The present invention relates to a catalyst for preparing syndiotactic polystyrene (sPS), which comprises a metallic titanium compound R1Ti (OR2R3)3 and alkyl aluminoxane, wherein R1 is cyclopentadienyl or cyclopentadienyl containing 1 to 5 C1 to C4 alkyl; R2 is aryl containing 6 to 12 carbon atoms; R3 is halogen. When the catalytic system is used for the syndiotactic polymerization of styrene, the catalytic system has high catalytic activity and high catalyzing efficiency; the maximum catalytic activity reaches 510kg of polymer/g of titanium per hour; the catalyst can be used for industrial production.

Description

The catalyzer of preparation syndiotactic polystyrene
Technical field
The present invention relates to prepare the catalyzer of syndiotactic polystyrene.
Background technology
Styrene polymer can be divided into random polystyrene (aPS), isotactic polyphenylacetylene (iPS) and syndiotactic polystyrene (sPS).The catalyst system that synthesis of syndiotactic polystyrene adopts organo-metallic titanium compound and poly-methylaluminoxane (MAO) to form usually, wherein organometallic compound mainly is a cyclopentadiene titanium compound.It is CpTiCl that document EP 210615, US5252693, JP0291104 and EP389981 etc. have reported structure 3/ MAO, Cp *TiCl 3/ MAO catalyst system is used for the situation of syndiotactic polymerization of phenylethylene, but its catalytic activity and catalytic efficiency are not high, and industrial application is undesirable.
Summary of the invention
Technical problem to be solved by this invention is to overcome catalytic activity and the not high problem of catalytic efficiency that exists in the above-mentioned document, and a kind of catalyzer of new preparation syndiotactic polystyrene is provided, and this catalyzer has advantages of high catalytic activity and catalytic efficiency.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of catalyzer for preparing syndiotactic polystyrene comprises metallocene titanium compound I and alkylaluminoxane II:
R 1Ti(OR 2R 3) 3 I
R in the formula 1For cyclopentadienyl or contain 1～5 C 1～4The cyclopentadienyl of alkyl;
R 2For containing the aryl of 6～12 carbon atoms;
R 3Be halogen;
R 4For containing the alkyl of 1～4 carbon atom;
N is the oligomerisation degree of alkylaluminoxane, and its value is 6～40;
Wherein the aluminium among the alkylaluminoxane II is 50～2000 to the mole ratio of metallocene titanium compound I, Ti and R 2Between have Sauerstoffatom to link to each other.
The preferred value of oligomerisation degree n is 10～30 in the technique scheme, also contains the triisobutyl aluminium component in the catalyzer, and with the molar ratio computing triisobutyl aluminium: alkylaluminoxane is 0.1～2, R 1Preferred version be cyclopentadienyl or pentamethyl-cyclopentadienyl, more preferably scheme is the pentamethyl-cyclopentadienyl.R 2Preferred version be the alkaryl that contains 6～12 carbon atoms, another preferred version is phenyl, indenyl or xenyl.R 3Preferred version for being selected from fluorine, chlorine, bromine or iodine, more preferably scheme is a chlorine.
Poly-alkylaluminoxane is prepared by control hydrolysis by aluminum alkyls.Reactants water can be the water that contains in the inorganic salt of crystal water, and the inorganic salt that contain crystal water can be CaCl 26H 2O, MgCl 26H 2O, CuSO 45H 2O, CaSO 42H 2O, Al 2(SO 4) 318H 2O, MgSO 47H 2O, FeSO 47H 2O, Ti (SO 4) 24H 2O, Ti 2(SO 4) 38H 2O and ZnSO 47H 2O etc.Trimethyl aluminium (TMA) is 1: 1～1: 3 with the mole ratio of water, and temperature of reaction is-20～100 ℃, and the reaction times is 10～40 hours.Aluminum alkyls commonly used has trimethyl aluminium, triethyl aluminum, triisobutyl aluminium etc.Concrete steps are: aluminum alkyls is pressed Al/H 2The O mole ratio is slowly to be added dropwise to Al in 1: 1～1: 2 under-20～0 ℃ 2(SO 4) 318H 2In the toluene mixture liquid of O, the dropping time is 0.5～4 hour.Reaction 5～40 hours is continued in elevated temperature to 20～100 ℃ gradually under this temperature then.Reaction mixture is solids removed by filtration under nitrogen protection, and solvent evaporated under reduced pressure gets white solid product, promptly obtains the alkylaluminoxane that structure is II.
The preparation method of metallocene titanium compound I is as follows: is that solvent reaction make with the hydrocarbon polymer by corresponding cyclopentadienyl titanous chloride and corresponding alkenyl alcohol in the presence of chlorine hydride absorbent.Chlorine hydride absorbent can be various aminated compoundss, wherein is advisable with trialkylamine, for example triethylamine.Hydrocarbon polymer can be aliphatic hydrocarbon or aromatic hydrocarbon, uses aromatic hydrocarbon better, for example benzene, toluene etc.Concrete steps are: the mixing solutions of triethylamine and corresponding alkenyl alcohol is slowly dropped in the benzole soln of corresponding cyclopentadienyl titanous chloride, the mole ratio of corresponding cyclopentadienyl titanous chloride and corresponding alkenyl alcohol is 1.0: 3.0, the mole ratio of corresponding cyclopentadienyl titanous chloride and triethylamine is 1.0: 3.0～4.0, temperature of reaction is 1～130 ℃, 2～48 hours reaction times.Solids removed by filtration under protection of inert gas, underpressure distillation are removed and to be desolvated, the crude product hexane extraction that obtains, remove volatile matter after, must the xanchromatic crystal.
Work as R 1Be pentamethyl-cyclopentadienyl, R 2Be phenyl, R 3Structural formula of compound is during for chlorine:
Through hydrogen nuclear magnetic resonance spectrogram and infrared spectra map analysis is said structure.
Its data are as follows:
Ultimate analysis (element analysis)
C 28H 27O 3Cl 3Ti：
Calcd.For
C 59.42％
H 4.77％
Cl?18.83％
Found
C 59.25％
H 4.79％
Cl?18.71％
The proton nmr spectrum
[HNMR?CDCl 3?TMS?intern]
δ6.75～7.25(m，12H，-(OPhHCl )3)
δ1.90～2.15(s，15H，Cp-CH 3)
Catalyst component I and II can be under protection of inert gas (for example nitrogen, argon gas etc.) under 0～50 ℃, preferably 30 ℃ are reacted earlier.
Polyreaction is preferably carried out between 60～90 ℃ under 30～100 ℃.In order to obtain the polymkeric substance of ideal performance, polymerization needs the regular hour, and by several hours, preferably 0.1～3 hour, the ideal polymerization time depended on polymerization temperature, solvent and other polymerizing condition from several minutes.The polyreaction mode can adopt solution polymerization, slurry polymerization and mass polymerization.For solution polymerization and slurry polymerization, the solvent of employing is aliphatic hydrocarbon or aromatic hydrocarbon, as hexane, heptane, hexanaphthene, benzene, toluene etc.The concentration of vinylbenzene in solvent is in 5～100% scopes.
The present invention adopts the Primary Catalysts of a kind of new metallocene titanium compound as the preparation syndiotactic polystyrene, make the catalytic activity of catalyzer reach 510 kg of polymer/gram titanium/hour, obtained effect preferably.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
Preparation of Catalyst
In the there-necked flask of 250 milliliters of exsiccant, N 2Pump drainage 3 times adds the 1.016 single luxuriant titanium of gram pentamethyl-trichlorine and 70 milliliters of benzene, from 30 milliliters of benzene of top dropping, 1.35 the mixture of gram para-chlorophenol and 1.1 gram triethylamines dripped off after 45 minutes, normal-temperature reaction is after 1 hour, reheat reacts after 2 hours to the benzene reflux temperature, stops heating, normal-temperature reaction 10 hours, reacting by heating is 2 hours once more, filters, filtrate is drained, and uses toluene, hexane solution recrystallization repeatedly, drains, get yellow crystals 1.74 grams, yield 88%.
[embodiment 2]
Preparation of Catalyst
In the there-necked flask of 250 milliliters of exsiccant, N 2Pump drainage 3 times adds the 2.10 single luxuriant titanium of gram pentamethyl-trichlorine and 70 milliliters of benzene, from 0 milliliter of benzene of top Dropwise 5,2.79 the mixture of gram para-chlorophenol and 2.4 gram triethylamines drips off reacting by heating 4 hours after 45 minutes, normal-temperature reaction is 10 hours again, reacting by heating 4 hours is once more filtered at last, and filtrate is drained, use hexane extraction, drain, get yellow crystals 3.5 grams, productive rate 85%.
[embodiment 3]
On in baking, 50 milliliters of two mouthfuls of bottles of exsiccant, use high-purity N 2Pump drainage 3 times, add 10 milliliters of commercial benzene vinyl monomers, induction stirring was injected triisobutyl aluminium 0.2 mmole with syringe after 20 minutes in 60 ℃ of oil baths, MAO 0.4 mmole, the metallocene-titanium catalyst 0.001 mmole reaction of embodiment 1 with ethanol-hydrochloric acid soln stopped reaction, was washed after 10 minutes, dry that powder solid 3.53 restrains, catalytic activity 443 kg of polymer/(the gram titanium. hour), a normality 96%, Mw=37 * 10 4
[comparative example 1]
On in baking, 50 milliliters of two mouthfuls of bottles of exsiccant, use high-purity N 2Pump drainage 3 times, add 10 milliliters of commercial benzene vinyl monomers, induction stirring was injected MAO 0.6 mmole with syringe after 20 minutes in 60 ℃ of oil baths, and the metallocene-titanium catalyst 0.001 mmole reaction of embodiment 1 is after 30 minutes, with ethanol-hydrochloric acid soln stopped reaction, washing, dry that powder solid 0.852 restrains, catalytic activity 35 kg of polymer/(the gram titanium. hour), between normality 95%, Mw=46 * 10 4
[embodiment 4]
On in baking, 50 milliliters of two mouthfuls of bottles of exsiccant, use high-purity N 2Pump drainage 3 times, add 10 milliliters of commercial benzene vinyl monomers, induction stirring was injected triisobutyl aluminium 0.2 mmole with syringe after 20 minutes in 60 ℃ of oil baths, MAO 0.6 mmole, the metallocene-titanium catalyst 0.001 mmole reaction of embodiment 2 with ethanol-hydrochloric acid soln stopped reaction, was washed after 10 minutes, dry that powder solid 3.78 restrains, catalytic activity 474 kg of polymer/(the gram titanium. hour), a normality 96%, Mw=30 * 10 4
[embodiment 5]
On in baking, 50 milliliters of two mouthfuls of bottles of exsiccant, use high-purity N 2Pump drainage 3 times, add 10 milliliters of commercial benzene vinyl monomers, induction stirring was injected triisobutyl aluminium 0.4 mmole with syringe after 20 minutes in 60 ℃ of oil baths, MAO 0.4 mmole, the metallocene-titanium catalyst 0.001 mmole reaction of embodiment 2 with ethanol-hydrochloric acid soln stopped reaction, was washed after 10 minutes, dry that powder solid 4.07 restrains, catalytic activity 510 kg of polymer/(gram titanium hour), a normality 96%, Mw=27 * 10 4
[comparative example 2]
On in baking, 50 milliliters of two mouthfuls of bottles of exsiccant, use high-purity N 2Pump drainage 3 times adds 10 milliliters of commercial benzene vinyl monomers, and induction stirring was injected triisobutyl aluminium 0.4 mmole, MAO 0.4 mmole, Cp with syringe after 20 minutes in 60 ℃ of oil baths *TiCl 30.001 mmole reaction (Cp after 10 minutes *Be the pentamethyl-cyclopentadienyl), with ethanol-hydrochloric acid soln stopped reaction, washing, dry that powder solid 0.41 restrains, catalytic activity 51 kg of polymer/(the gram titanium. hour), a normality 94%, Mw=15 * 10 4
[embodiment 6]
On 10 liters of mechanical stirring kettles, after 8 hours, be cooled to 60 ℃, N 90 ℃ of bakings earlier 2Pump drainage 3 times adds styrene monomer 2375 grams, stirs after 30 minutes, contain 52.8 mmole triisobutyl aluminiums with the syringe injection, 105.6 mmole MAO, the metallocene-titanium catalyst toluene solution of 0.264 mmole embodiment 1 is at 300 rev/mins of following stirring reactions after 3 hours, with ethanol-hydrochloric acid soln stopped reaction, washing, dry that powder solid 1950 restrains catalyst efficiency 154 kg of polymer/(gram titanium), between normality 97%, Mw=34 * 10 4

Claims (9)

1, a kind of catalyzer for preparing syndiotactic polystyrene comprises metallocene titanium compound I and alkylaluminoxane II:
R 1Ti(OR 2R 3) 3 I
Figure C021113010002C1
R in the formula 1For cyclopentadienyl or contain 1～5 C 1～4The cyclopentadienyl of alkyl;
R 2For containing the aryl of 6～12 carbon atoms;
R 3Be halogen;
R 4For containing the alkyl of 1～4 carbon atom;
N is the oligomerisation degree of alkylaluminoxane, and its value is 6～40;
Wherein the aluminium among the alkylaluminoxane II is 50～2000 to the mole ratio of metallocene titanium compound I, Ti and R 2Between have Sauerstoffatom to link to each other.
2, the catalyzer of preparation syndiotactic polystyrene according to claim 1 is characterized in that R 1Be cyclopentadienyl or pentamethyl-cyclopentadienyl.
3, the catalyzer of preparation syndiotactic polystyrene according to claim 2 is characterized in that R 1Be the pentamethyl-cyclopentadienyl.
4, the catalyzer of preparation syndiotactic polystyrene according to claim 1 is characterized in that R 2For containing the alkaryl of 6～12 carbon atoms.
5, the catalyzer of preparation syndiotactic polystyrene according to claim 1 is characterized in that R 2Be phenyl, indenyl or xenyl.
6, the catalyzer of preparation syndiotactic polystyrene according to claim 1 is characterized in that R 3Be selected from fluorine, chlorine, bromine or iodine.
7, the catalyzer of preparation syndiotactic polystyrene according to claim 6 is characterized in that R 3Be chlorine.
8, the catalyzer of preparation syndiotactic polystyrene according to claim 6 is characterized in that the value of the oligomerisation degree n of alkylaluminoxane is 10～30.
9, the catalyzer of preparation syndiotactic polystyrene according to claim 1 is characterized in that also containing in the catalyzer triisobutyl aluminium component, and with the molar ratio computing triisobutyl aluminium: alkylaluminoxane is 0.1～2.
CN 02111301 2002-04-10 2002-04-10 Catalyst for preparing syndiotacti polystyrene Expired - Fee Related CN1207315C (en)

Priority Applications (2)

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CN 02111301 CN1207315C (en) 2002-04-10 2002-04-10 Catalyst for preparing syndiotacti polystyrene
US10/410,036 US6921734B2 (en) 2002-04-10 2003-04-09 Titanocene complexes and its catalyst for preparing syndiotactic polystyrene

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 02111301 CN1207315C (en) 2002-04-10 2002-04-10 Catalyst for preparing syndiotacti polystyrene

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CN1207315C true CN1207315C (en) 2005-06-22

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